Of basel



Patented Aprr'19, i927.

(UNITED, STATES PATENT oFricE.

HEBMANN rnrrz'sonn; nnoann'x'nom unnacnna, HANS GUBLER, AND or'ro mean,

or BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY or cnmncar. INDUSTRY m l BASLE, OF BASEL. SWITZERLAND.

I PROCESS OF MAKING INTERMEDIATE PRODUCTS FOR THE MANUFACTURE OF AZO DYES.

I f i 80' Drawing. Applicationt-filed July 20, 1928, Serial No. 652,858, and in Switzerland September 7,1922.

intermediate products of the general fo r-- mula wherein R means an aromatic complex which contalns one of a group of auxochromes including h i -OH-,-CH 00- N- N-.

- 'R|. a c0 (wherein R, and-R represent the same or of the cyanuric complex by one of a group of connecting links" which. contains -O- and 'N, y a halogen or a hydrogen atom or a radical, the hydrogenand the radical being linked to the carbon atom of. the cyanuric nucleus by one linking, such as or O, and n a whole number not higher than the number of the mobile hydrogen atoms originally present in the molecule correspondingwith Q.

It has been found that some 'of these intermediate products, where Q, represents a radical which does not carry one of a group 4 of auxochromes including (wherein B and R represent the same or difierent alkyl, aryl or aralkyl radicals or In a first phase at least one molecular proportion of a cyanuric t-rihalide is condensed with one molecular proportion of a compound containing a mobile atom of hydro gen which is linked to an oxygen or nitrogen atom, but not carryin besides one of a group of auxochromes inc uding diflerent alkyl, aryl or aralkyl radicals or,

products containing at least one cyanuric nucleuswhich carries two mobile atoms of (wherein R and R represent thesame or halogen. In a secondpllase'any number of amino group, and which contains, besides this aminogroup, one of a group of au xo-' chromes including- (wherein R and R represent. the same or 1 'diflerent alkyl, aryl oraralkyl radicals or a'hydrogen' atom) and at least one strong acid group, such as a sulfo group or a carboxylic group.

These condensations may be carried out 1n most cases by stirring successivel together the components in a suitable d1 uent as which water is very appropriate. The

- course of the reaction may be followed, also in this case, by the quantity of hydrogen halide obtained, by the formation of a precipitate or a clear solution, or by the disappearance of the components.

4 Eat-11mph: 1.

21 arts of sodium 1 3-phenylenediamine- 4-sul onate are dissolved in 300 parts of water. To this solution there are added 14.6 parts of the condensation product from 1 molecular proportion of cyanuric chloride while the whole is and '2 molecular roportions of ammonia, Boiled for one hour. The liquid is then cooled, acidified and filtered. The new tertiary condensation product thus formed from .1 molecular proportion of cyanuric chloride, 2 molecular proportions of ammonia and 1 molecular proportion of 1 3-phenylenediamine-4-sulfon1c acid forms a crystallized owder dissolving easily in water, with diifiiiulty in alkalies.

Example 2.

dGIlSEtlOIl product is formed from one monot -O21;- \N% -3 OgH If for instance the solution obtained as described in the first paragraph of this example is heated with one molecular pro ortion of aniline, there is formed the tertiary condensation product from one molecular roportion of cyanuric chloride, one molecuar proportion of 2:5-aminonaphthol-7-sulionic acid, one molecular proportion of sulfanilic acid and one melocular proportion of aniline. This product is soluble with much greater difliculty than the secondary com- .pound of the first para raph.

Other secondary con ensation products, as for instance, the one from 1 molecular proportion of cyanuric chloride, 1 molecular roportion of sulfanilic acid and one molecuar proportion of ammonia, or the condensation product from 1 molecular proportion of oyanuric chloride 'and 2 molecular proportions of sulfanilic acid react in the same or in a similar way.

lecular proportion of cyanuric chloride, one

molecular proportion of sulfanilic acid and 1 molecular proportion of 2.5-aminonaph thol-7-sulfonic acid. By adding common salt the product is thrown out.

This compound corresponding very probably with the formula OgH W H L SOIH 3O N N HOa L L Example 3.

26.2 parts of sodium 2:5-aminona-phthol- 7-sulfonate and 14 parts of crystallized sodium acetate are dissolved in 500 parts of boiling water and treated at this temperature with 14.6 parts of the secondary condensation product, from 2 molecular proportions of ammonia and one molecular proportion of cyanuric chloride. This compound dissolves gradually and the tertiary condensation product thus obtained from one molecular proportion of cyanuric chlori e, 2 molecular proportions of ammonia and one molecular pro ortion of 2:5-aminonaphthol-7-sulfonic aci thus obtained, separates in form of or stals. It is a greyish white powder disso vin in cold water with difiiculty, more easil 1n hot water, its alkaline solutions do not uoresce. The condensation product from 1 molec- 18.5 parts of cyanuric chloride are suspended in1500 parts of iced water, treated with a solution of 23.2 parts sodium phenolate in 500 parts of water and stirred until .-the ,tormation of the secondary condensation product from one molecular proportion of cyanuric chloride and 2 molecular proportions of phenol is achieved.v 26.1 parts of 2: 8-aminonaphthol-6-sulfonic acid are then added, while the whole' is stirred for some time in a reflux apparatus at the boiling temperature. The mixture is then cooled and the tertiary condensation prodnot from one molecular proportion of cyanuric chloride, 2 molecular proportions of phenol and 1 molecular proportion of 2: 8-

, aminonaphthol-fi-sulfonic acid thus obtained corresponding with the formula Qdr isthrown out with hydrochloric acid. It is a grey powder, easily soluble in a solution of sodium carbonate.

Instead of sodium 2:8-aminonaphthol-6 sulfonate, other neutral salts of the aminonaphthol-sulfonic acids may be condensed in order to produce other tertiary condensation products, as for instance, the salts of the 2:5-aminonaphthol-7-sulfonic acid and I those of the 1:8-aminonaphthol-3:fi-disulr fonic acid The secondary condensation product from one molecular proportion of which is isolated by acidifying and addicyanuric chloride and 2'molecular proper tlons of henol, prepared in this example as interme late product, melts, if crystallized from alcohol, at -1'18120 C.

Ewai nple 5.

18.5 parts ofi'cyanuric chlorideare suspendedin water, treated with 17.4 parts of m-nitraniline hydrochloride and stirred, in

. the cold, until the m-nitraniline has almost completely disappeared. The crystallized condensation product thus obtained is then filtered, dissolved in acetone and the solution run gradually into a solution of 319 parts of l 8-aminonaphthol-3 6-disulfonic acid and 106 parts of sodium carbonate in 5000 parts of water. -The :whole is still stirred until the aminonaphthol sulfonic acid has almost completely disappeared and the condensation product from one molecular proportion of cyanuric chloride; one

molecular proportion of n'l-nitraniline and one molecular proportion of 1:8-aminonaphthol 3:6-disulionic acid thus formed is thrown out by lueans of common salt. It corresponds very probably withthe formula o,uO-N-ii yi-m-n on t N y p HOaS soar The third atom of chlorine of this product may be exchanged for residues of any kind.

Example 6.

Intoa solution of the primar condensation product from 18.5 parts or cyanuric chloride and 20 parts of p-phenylenediamine sulfonic acid there is run. a solution of 18.5 parts of cyanuric chloride dissolved in a small quantit of acetone while the whole is'stirredunt' 3.6 parts of hydrochloric acid are freed. The 'di-primary condensation product thus obtained is filtered. It forms a grey owder and contains still a mobile atoms 0 chlorine. I

If the neutral solution of its sodium salt is stirred for some time, with 40 parts of -phenylenediamine sulfonic acid, there is ormed the (Ii-secondary condensation product of the general formula:

tion of common salt.

What we claim is: The herein described rocess of making intermediate products of t e general formula N ay- .Q I 11 wherein R means an aromatic complex which contains one of a group of auxochromes includmg a radical, the hydrogen and the radical being linked to the carbon atom of the cyanurio nucleus by one linking, such as -N- or -O, and n a whole number not higher than the number of the mobile hydrogen atoms originally present in the molecule corresponding with Q, which consists in condensing, in a first phase, at least one molecular proportion of a cyanuric trihalide with one molecular roportion of a compound containing a mo ile atom of hydrogen which is linked to an oxygen or a nitrogen atom but not carrying besides one of a group 0% auxochromes including (wherein R and R represent the same or difi'erent alkyl, aryl or aralkyl radicals or a hydrogen atom), then causing to react, in a second phase, any number of the atoms of halogen belonging to the products obtained in the first phase with compounds carrying mobile atoms of hydrogen which are linked to oxygen or nitrogen atoms, whereby at least one of the compounds which are employed in the second phase, firstly, contains the mobile hydro en atom linked to a nitrogen atom, secondly, contains still one of a group of auxochromes including (wherein R and R represent the same or -on, -cH,oo-,

dilferent alkyl, aryl or aralkyl radicals or 7 hydrogen atoms), thirdly, contains a strong acid group, one phase at least being carried out in water.

In witness whereof we have hereunto signed our names this 6th day of July 1923.

HERMANN FRITZSCHE. EDUARD KRUMMENACHER. HANS GUBLER. OTTO KAISER. 

